Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons

ABSTRACT

A well treatment composition is well-designed for the simultaneous enhancement of the production of both liquid and gaseous hydrocarbons from the same reservoir on a non-selective basis. The well treatment composition includes a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines. The well treatment composition also includes a first solvent, a second solvent and water. Methods for using the well treatment composition include the steps of emplacing the well treatment composition into wells having high and low gas-to-oil ratios.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/644,419 entitled COMPOSITIONS AND METHODS FOR ENHANCEMENT OF PRODUCTION OF LIQUID AND GASEOUS HYDROCARBONS, filed May 8, 2013, the disclosure of which is herein incorporated by reference.

FIELD OF THE INVENTION

The present invention generally relates to the production of petroleum and more particularly to compositions and processes for improving the recovery of liquid and gaseous forms of petroleum from a subterranean geological formation.

BACKGROUND OF THE INVENTION

For many years, petroleum has been recovered from subterranean reservoirs through the use of drilled wells and production equipment. Petroleum hydrocarbons may be produced in a variety of forms, including liquid crude oil, natural gas and light condensates. To enhance the recovery of petroleum, a number of technologies have been developed. Common well stimulation techniques include hydraulic fracturing, water flooding and acidizing operations. Although liquid and gaseous products are typically encountered together, it may be economically desirable to enhance the production of one form of hydrocarbons over another. For example, economic factors may encourage the shift from a predominantly gas-focused production to a production that favors liquid crude oil. Because crude oil and natural gas have very different physical properties, and thus move differently through the porous media of the subterranean formation, the chemicals used for stimulating the well for the purpose of enhancing gas production may not work as effectively in enhancing oil production. As a result, prior art well stimulation and enhancement products have been formulated to recover a particular form of hydrocarbon, i.e., natural gas or liquid crude oil.

To permit the production of multiple forms of hydrocarbons from a given reservoir, well operators are required to use and stock multiple chemicals for treating the same well. Such practice also often requires additional equipment for handling multiple types of chemicals. The use of multiple treatment chemicals increases the cost and complexity of operating the well. Therefore, having a single stimulation product that enhances fluid recovery of multiple forms of hydrocarbons is desirable. It is to these and other objects that the present invention is directed.

SUMMARY OF THE INVENTION

In a preferred embodiment, the present invention includes a well treatment composition that is suitable for the simultaneous enhancement of the production of both liquid and gaseous hydrocarbons from the same reservoir on a non-selective basis. In a specific embodiment, the method provides for increasing the production of oil from a first well having a high gas-to-oil ratio and the production of gas from a second well having a low gas-to-oil ration. The method preferably includes the steps of providing a complex nanofluid additive, emplacing the complex nanofluid additive into the first well and emplacing the same complex nanofluid additive into the second well.

In another aspect, the novel well treatment composition includes a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines. The well treatment composition also includes a first solvent, a second solvent and water. The first solvent is preferably suspended as an internal phase with an external phase created by the water by the first and second surfactants.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In a preferred embodiment, the present invention includes a well treatment composition that is suitable for the simultaneous enhancement of the production of both liquid and gaseous hydrocarbons from the same reservoir on a non-selective basis. In this way, formulations of the preferred embodiments can be used to improve the recovery of liquid and gaseous hydrocarbons during a single treatment operation. The compositions of the preferred embodiments can be used to treat predominantly oil-producing wells to achieve production of gas at commercially viable rates, and to treat predominantly gas-producing wells to achieve production of oil at commercially viable rates.

In preferred embodiments, the complex nanofluid additives of the present invention include: (i) a first surfactant; (ii) a second surfactant, where the second surfactant includes at least one ethoxylated/propoxylated alkylene or alkyl amine surfactant; (iii) one or more solvents with limited solubility in water; (iv) one or more co-solvents; and (v) water. The inventive well treatment additive is characterized as a complex nanofluid that includes at least two normally immiscible solvents stabilized by one or more selected surfactants. In a preferred embodiment, the complex nanofluid includes an internal phase hydrocarbon-based organic solvent distributed in an aqueous external phase.

Preferred conventional surfactants include mixtures of ethoxylated vegetable oils and ethoxylated alcohols. In a more particularly preferred embodiment, the selected surfactant or surfactant mixture has a hydrophile-lipophile balance (HLB) value of between 8 and 18. In a particularly preferred embodiment, the surfactant component is an ethoxylated alcohol. In a more preferred embodiment, the surfactant component is an ethoxylated C8-C18 alcohol. In a still more preferred embodiment, the surfactant component is an ethoxylated C8-C18 alcohol with 5-20 moles of ethylene oxide (EO). In a particularly preferred embodiment, the surfactant component is an ethoxylated vegetable oil. U.S. Pat. No. 7,380,606 issued to Pursley, et. al on Jun. 3, 2008 entitled “Composition and Process for Well Cleaning,” which is incorporated herein by reference, discloses several surfactants that function as the surfactant component of the complex nanofluid additive. In certain applications, it may be desirable for the surfactant component to include a mixture of different surfactants and surfactant packages. A particularly preferred surfactant package includes C8-C18 linear alcohol alcoxylates, midrange primary, secondary and tertiary alcohols with between 1 and 10 carbon atoms, C2-C10 glycols, and can also include between 5-30 wt % water. Additionally, the surfactant package can include an ethoxylated vegetable oil.

The second surfactant component is preferably an amine-based surfactant selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines. The ethoxylated/propoxylated alkylene or alkyl amine surfactant component preferably includes more than one nitrogen atom per molecule. Suitable amines include ethylenediaminealcoxylate and diethylenetriaminealcoxylate.

Preferred solvents include organic solvents and more particularly, citrus terpenes. D-limonene provides a suitable and desirable solvent that is normally immiscible in water.

The co-solvent component of the complex nanofluid additive may include a short-chain alcohol having a linear or branched chain with less than about 6 carbon atoms. The co-solvent component may further include glycols and mutual solvents or mixtures of thereof. Unlimited examples of suitable alcohols and glycols include methanol, ethanol, 1-propanol, 2-propanol, isomeric butanols, ethylene glycol, triethlyne glycol, propylene glycol, ethylene glycol monobutyl ether.

Particularly preferred embodiments contain from about 5% to about 40% by weight water, from about 0.05 to about 20% by weight solvent and from about 30% to about 75% by weight of nonionic surfactant mixture, in which a first surfactant is a surfactant with a hydrophile-lipophile balance (HLB) greater than 7, and a second surfactant is an ethoxylated-propoxylated alkylene or alkyl amine with more than one nitrogen atom. In a more particularly preferred embodiment, the amine surfactant component is present in a weight ratio to other surfactants from about 0.01 to about 5 and comprises less than 50% of the total additive formulation.

Additives of the preferred embodiments may also contain from about 10% to about 30% by weight of co-solvents. Additives prepared in accordance with preferred embodiments present a colloidal system with droplets having the mean diameter of less than 200 nm when diluted with an aqueous carrier fluid in a ratio from about 1:10000 to about 1:10. In a particularly preferred embodiment, the solvent to water weight ratio is less than about 2.

The preferred embodiments of the complex nanofluid additives can be prepared by mixing individual components or in-situ by diluting solvent-surfactant blends with a selected carrier fluid, fracturing fluid or acidizing fluid in a batch-tank or on-the-fly during the treatment operation.

The following provides a description of laboratory investigations used to establish the efficacy of the inventive complex nanofluid additives. These experiments included an analysis of the effectiveness of the additives on oil-brine displacement and gas-brine displacement. The complex nanofluid additives of the preferred embodiments were compared against prior-art reference additives.

For the oil-brine displacement experiments, a 25 cm long, 2.5 cm diameter capped glass chromatography column was packed with 77 grams of 100 mesh sand. The column was left open on one end and a PTFE insert containing a recessed bottom, 3.2 mm diameter outlet, and nipple was placed into the other end. Prior to placing the insert into the column, a 3 cm diameter filter paper disc (Whatman, #40) was pressed firmly into the recessed bottom of the insert to prevent leakage of 100 mesh sand. A 2″ piece of vinyl tubing was placed onto the nipple of the insert and a clamp was fixed in place on the tubing prior to packing. The columns were gravity-packed by pouring approximately 25 grams of the brine (or brine with chemical treatment) into the column followed by a slow, continuous addition of sand.

After the last portion of sand had been added and was allowed to settle, the excess of brine was removed from the column so that the level of liquid exactly matched the level of the sand. Pore volume in the packed column was calculated as the difference in mass of fluid prior to column packing and after the column had been packed. Three additional pore volumes of brine were passed through the column. After the last pore volume was passed, the level of brine was adjusted exactly to the level of sand bed. Light condensate oil was then added on the top of sand bed to form the 5 cm oil column above the bed. Additional oil was placed into a separatory funnel with a side arm open to an atmosphere.

Once the setup was assembled, the clamp was released from the tubing, and timer was started. Throughout the experiment the level of oil was monitored and kept constant at a 5 cm mark above the bed. Oil was added from the separatory funnel as necessary, to ensure this constant level of head in the column. Portions of effluent coming from the column were collected into plastic beakers over a measured time intervals. The amount of fluid was monitored. When both brine and oil were produced from the column, they were separated with a syringe and weighed separately. The experiment was conducted for 3 hours at which the steady-state conditions were typically reached. The cumulative % or aqueous fluid displaced from the column over 120 minute (2 hour) time period was determined.

For the gas-brine displacement experiments, a 51 cm long, 2.5 cm in diameter capped glass chromatography column was filled with approximately 410±20 g of 20/40 mesh Ottawa sand and a brine (or brine containing chemical treatment). To ensure uniform packing, small amounts of proppant were interchanged with small volumes of liquid. Periodically the mixture in the column was homogenized with the help of an electrical hand massager, in order to remove possible air pockets. Sand and brine were added to completely fill the column to the level of the upper cap. The exact amounts of fluid and sand placed in the column were determined in each experiment. The column was oriented vertically and was connected at the bottom to a nitrogen cylinder via a gas flow controller pre-set at a flow rate of 60 cm³/min. The valve at the bottom was slowly opened and liquid exiting the column at the top was collected into a tarred jar placed on a balance. Mass of collected fluid was recorded as a function of time by a computer running a data logging software. The experiments were conducted until no more brine could be displaced from the column. The total % of fluid recovered was then calculated.

For these experiments, complex nanofluid additives were prepared in the laboratory by mixing the selected terpene solvent, water, conventional nonionic surfactant with HLB>7, and ethoxylated and propoxylated alkylene or alkyl amine surfactant in ratios described above. All of these constituent components are commercially available from a variety of sources. Typically, the components were mixed together in the order: water, alcohol, nonionic surfactant, ethoxylated-propoxylated alkylene or alkyl amine, and lastly citrus terpene solvent. Other orders of addition are also suitable. The mixtures were then agitated on a magnetic stirrer for 5-10 minutes.

The complex nanofluid additives were then diluted to use concentrations of 1 or 2.0 gallons per 1000 gallons with 2% KCl brine and these diluted fluids were used in gas-oil and gas-brine displacement experiments described above. The selected concentrations are those typically suitable, but other concentrations can be used by those skilled in the art. In addition to the compositions of the present invention, several compositions of the prior art were also prepared. Notably, these prior art reference compositions did not contain the ethoxylated-propoxylated alkylene or alkyl amine component. The reference additives are presented in Table 1 below:

TABLE 1 Reference Additives Reference complex nanofluid #1 (NF#1) Deionized water: 11.9 wt % Ethoxylated alcohol nonionic surfactant package 75.1 wt % co-solvent  8.0 wt % Citrus terpene:  5.0 wt % Reference complex nanofluid #2 (NF#2) Deionized water:  15 wt % Ethoxylated alcohol nonionic surfactant package 36.4 wt % Co-solvent 26.5 wt % Citrus terpene: 22.1 wt % Reference complex nanofluid #3 (NF#3) Deionized water: 22.5 wt % co-solvent    35.1% Pluronic ® surfactant 13.5 wt % Ethoxylated castor oil: 13.5 wt % Citrus terpene: 15.4 wt %

The complex nanofluid additives of the preferred embodiments were prepared according to the examples set forth in Table 2:

TABLE 2 Inventive Complex Nanofluid Additives Example 1 Deionized water 16.2 wt % Ethoxylated alcohol surfactant package 56.1 wt % 2-propanol co-solvent 11.5 wt % Citrus terpene  4.5 wt % Ethylenediaminealcoxylate 11.7 wt % Example 2 Deionized water 16.2 wt % Ethoxylated alcohol surfactant package 56.1 wt % co-solvent 11.5 wt % Citrus terpene  4.5 wt % Diethylenetriaminealcoxylate 11.7 wt % Example 3 Deionized water  6.4 wt % Ethoxylated alcohol surfactant package 60.1 wt % co-solvent 11.5 wt   Citrus terpene   7 wt % Ethylenediaminealcoxylate  15 wt % Example 4 Deionized water  0.4 wt % Ethoxylated alcohol surfactant package 66.1 wt % 2-propanol co-solvent 11.5 wt % Citrus terpene   7 wt % Ethylenediaminealcoxylate  15 wt %

Each of the reference additives and inventive additives were evaluated using the test protocols set forth above. The results of these experiments are summarized in Table 3 below as a percentage of the recovery of brine displacement by gas and brine displacement by oil. Each reference additive and inventive additive was utilized in a concentration range of between 1 gpt and 2 gpt.

TABLE 3 Effectiveness of Effectiveness of brine displacement brine displacement Sample by gas by oil Reference NF#1 1gpt 80% 38% Reference NF#2 2 gpt 80% 43% Reference NF#3 1.5 gpt 25% 80% Example 1 1 gpt 75% 88% Example 2 1 gpt 81% 84% Example 3 1 gpt 59% 88% Example 4 1 gpt 72% 91%

Based on the results summarized above, it is clear that Reference Additives Nos. 1 and 2 are well-suited for enhancing gas recovery but are not as effective for the recovery of liquid hydrocarbons. Reference Additive No. 3 performed well during the liquid recovery test but did not displace a significant percentage of hydrocarbons during the gas test. Thus, the reference formulations did not demonstrate an ability to effectively recover both liquid and gaseous hydrocarbons. In contrast, the inventive complex nanofluid additives demonstrated effective recovery of both liquid and gaseous hydrocarbons. The ability of these inventive formulations to enhance the recovery of both liquid and gaseous hydrocarbons represents a significant advancement over the prior art.

It is clear that the present invention is well adapted to carry out its objectives and attain the ends and advantages mentioned above as well as those inherent therein. While presently preferred embodiments of the invention have been described in varying detail for purposes of disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are encompassed within the spirit of the invention disclosed and as defined in the written description. For example, surfactant and surfactant mixture selections can be modified and changed to take into account varying reservoir conditions. 

What is claimed is:
 1. A method of treating a plurality of hydrocarbon-producing wells, wherein a first of the plurality of hydrocarbon-producing wells has a high gas-to-oil ratio and a second of the hydrocarbon-producing wells has a low gas-to-oil ratio, the method comprising the steps of: providing a complex nanofluid additive; emplacing the complex nanofluid additive into the first of the plurality of hydrocarbon-producing wells to lower the gas-to-oil ratio; and emplacing the complex nanofluid additive into the second of the plurality of hydrocarbon-producing wells to raise the gas-to-oil ratio.
 2. The method of claim 1, wherein before the providing a complex nanofluid additive step, the method further comprises the steps of: providing a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines; mixing the first surfactant with the second surfactant to form a surfactant mixture; adding a first solvent and a second solvent to the surfactant mixture to form a solvent-surfactant mixture; adding water to the solvent-surfactant mixture to form an emulsified solvent-surfactant mixture; and adding the emulsified-solvent surfactant mixture to a carrier fluid to form the complex nanofluid additive.
 3. The method of claim 1, wherein before the providing a complex nanofluid additive step, the method further comprises the steps of: providing a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines; mixing the first surfactant with the second surfactant to form a surfactant mixture; adding a first solvent and a second solvent to the surfactant mixture to form a solvent-surfactant mixture; and adding water to the solvent-surfactant mixture to form an emulsified solvent-surfactant mixture, wherein the emulsified solvent-surfactant mixture comprises a concentrated form of the complex nanofluid additive.
 4. A method for increasing the production of oil from a first well having a high gas-to-oil ratio and the production of gas from a second well having a low gas-to-oil ratio, the method comprising the steps of: providing a complex nanofluid additive; emplacing the complex nanofluid additive into the first well; and emplacing the complex nanofluid additive into the second well.
 5. The method of claim 4, wherein before the providing a complex nanofluid additive step, the method further comprises the steps of: providing a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines; mixing the first surfactant with the second surfactant to form a surfactant mixture; adding a first solvent and a second solvent to the surfactant mixture to form a solvent-surfactant mixture; adding water to the solvent-surfactant mixture to form an emulsified solvent-surfactant mixture; and adding the emulsified-solvent surfactant mixture to a carrier fluid to form the complex nanofluid additive.
 6. The method of claim 4, wherein before the providing a complex nanofluid additive step, the method further comprises the steps of: providing a first surfactant and a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines; mixing the first surfactant with the second surfactant to form a surfactant mixture; adding a first solvent and a second solvent to the surfactant mixture to form a solvent-surfactant mixture; and adding water to the solvent-surfactant mixture to form an emulsified solvent-surfactant mixture, wherein the emulsified solvent-surfactant mixture comprises a concentrated form of the complex nanofluid additive.
 7. A well treatment composition useful for treating oil and gas wells having a high gas-to-oil ratio and oil and gas wells having a low gas-to-oil ratio, the composition comprising: a first surfactant; a second surfactant, wherein the second surfactant is selected from the group consisting of ethoxylated alkylene amines, ethoxylated alkyl amines, propoxylated alkylene amines, propoxylated alkyl amines, ethoxylated-propoxylated alkylene amines and ethoxylated-propoxylated alkyl amines; a first solvent; a second solvent, wherein the second solvent is a co-solvent; and water.
 8. The well treatment composition of claim 7, wherein the second surfactant is ethylenediaminealcoxylate.
 9. The well treatment composition of claim 7, wherein the second surfactant is diethylenetriaminealcoxylate.
 10. The well treatment composition of claim 7, wherein the first surfactant includes an ethoxylated alcohol.
 11. The well treatment composition of claim 10, wherein the first surfactant includes an ethoxylated alcohol having between 8 and 18 carbon atoms and between 5 and 20 moles of ethylene oxide.
 12. The well treatment composition of claim 7, wherein the first solvent is immiscible with water and suspended by the first and second surfactants as an internal phase within an external aqueous phase.
 13. The well treatment composition of claim 7, wherein the second solvent is a co-solvent selected from the group consisting of short-chain alcohols and glycols.
 14. The well treatment composition of claim 7, further comprising a carrier fluid.
 15. The well treatment composition of claim 7, wherein the first solvent, second solvent, first surfactant and second surfactant are emulsified as an oil-internal emulsion where the first solvent is suspended within the external water phase by the first and second surfactants.
 16. The well treatment composition of claim 7, wherein the well treatment composition comprises: up to about 90% by volume of the first surfactant, wherein the first surfactant is selected from the group consisting of nonionic surfactants, cationic surfactants, and anionic surfactants; up to about 16% by volume of the second surfactant, wherein the second surfactant is selected from the group consisting of ethylenediaminealcoxylate and diethylenetriaminealcoxylate; up to about 10% by volume of the first solvent, wherein the first solvent is d-limonene; up to about 25% by volume of the second solvent, wherein the second solvent comprises a co-solvent or a mixture of co-solvents; and up to about 30% by volume water. 